EP0283759B1 - Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung - Google Patents

Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung Download PDF

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Publication number
EP0283759B1
EP0283759B1 EP88102880A EP88102880A EP0283759B1 EP 0283759 B1 EP0283759 B1 EP 0283759B1 EP 88102880 A EP88102880 A EP 88102880A EP 88102880 A EP88102880 A EP 88102880A EP 0283759 B1 EP0283759 B1 EP 0283759B1
Authority
EP
European Patent Office
Prior art keywords
red phosphorus
phosphorus
melamine
stabilized
listed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88102880A
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German (de)
English (en)
French (fr)
Other versions
EP0283759A1 (de
Inventor
Horst Dr. Staendeke
Ursus Dr. Thümmler
Wilhelm Dr. Adam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT88102880T priority Critical patent/ATE54433T1/de
Publication of EP0283759A1 publication Critical patent/EP0283759A1/de
Application granted granted Critical
Publication of EP0283759B1 publication Critical patent/EP0283759B1/de
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/003—Phosphorus
    • C01B25/006—Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]

Definitions

  • the present invention relates to stabilized, powdery, free-flowing red phosphorus from phosphor particles with a particle size of at most 2 mm, and a method for producing the product according to the invention.
  • Red phosphorus is known to be obtained by fluorescent conversion of the yellow phosphor into the more stable red modification.
  • the raw, red phosphorus with a content of about 0.5-1.5% by mass of yellow phosphorus forms a compact mass after the reaction has ended. It is ground under an inert gas atmosphere and freed of yellow phosphorus in aqueous suspension by boiling with dilute sodium hydroxide solution (Ullmanns Encyklopadie der Technische Chemie, 3rd edition, 13th volume, 1962, phosphorus, pages 517/518, publisher Urban and Schwarzenberg, Kunststoff / Berlin ).
  • the conversion has recently been carried out in rotating reactors, with the red phosphorus being obtained as a powder.
  • the aqueous suspension of red phosphorus (EP-B 00 15 384) removed from the reactor is heated with steam in stirred vessels and the residual portion of about 0.1% by mass of yellow phosphorus is removed by adding sodium hydroxide solution in portions.
  • Red phosphorus is required in pyrotechnics and in the production of matchstick surfaces and is used as a flame retardant for plastics such as Polyamides or polyurethanes.
  • the object was therefore to improve the insufficient oxidation stability of the red phosphorus by stabilization.
  • stabilization is understood here to mean a measure which gives red phosphorus better protection against atmospheric influences and thus, for example contributes to a lower formation of oxo acids of phosphorus and of phosphorus hydrogen during storage or further processing.
  • Aluminum hydroxide has already been proposed for stabilizing red phosphorus (Gmelins Handbuch der inorganic Chemie, 8th edition, 1964, volume Phosphor, Part B, page 83, Verlag Chemie, Weinheim / Bergstrasse). The latter is precipitated on the phosphor particles by successive addition of 10% aqueous solutions of sodium hydrogen carbonate and aluminum sulfate heated to 55-60 ° C. The aqueous suspension is then filtered and the filter residue is dried.
  • This procedure has the disadvantage that in order to achieve a sufficient stabilizing effect, undesirably large amounts of aluminum hydroxide have to be used, so that the phosphorus is contaminated to an unacceptable degree in view of its further use in a wide variety of fields of application.
  • DE-A 2813 151 proposes using a mixture of aluminum hydroxide and lead hydroxide to stabilize red phosphorus.
  • DE-C 26 25 674 discloses an agent which enables the use of red phosphorus in plastic without the release of hydrogen phosphide due to the processing temperatures of the plastic and the presence of small amounts of water or moisture in the plastic to be processed.
  • the agent comprises epoxy resins which envelop the phosphor particles, the proportion of the resins being 5-50% by mass.
  • DE-C 29 45 118 claims stabilized, powdery, red phosphorus, consisting of phosphor particles with a particle size of at most 2 mm and an oxidation stabilizer, which uses a mixture of an epoxy resin and aluminum hydroxide, the oxidation stabilizer in the form of a phosphor particle wrapped in a thin layer.
  • the invention now relates to stabilized, powdery red phosphorus made of phosphor particles with a particle size of at most 2 mm, the surface of the phosphor particles being covered with a thin layer of an oxidation stabilizer, and the oxidation stabilizer consisting of at least one metal hydroxide which is sparingly or insoluble in water and consists of a polycondensation product consists of melamine and formaldehyde.
  • the total amount of the oxidation stabilizer is 1.1 to 25% by mass, based on the amount of red phosphorus.
  • the metal hydroxide content is 0.1 to 5% by mass and the melamine / formaldehyde resin content is 1 to 20% by weight, in each case based on the amount of red phosphorus.
  • hydroxides of aluminum, silicon, titanium, chromium, manganese, zinc, germanium, zirconium, niobium, cadmium, tin, lead, bismuth and / or cerium are used as metal hydroxide according to the invention and advantageously.
  • the process for the preparation of the stabilized, powdery, red phosphorus consists in introducing a water-soluble metal salt into an aqueous suspension of the red phosphorus, setting a pH value of 4-9 depending on the optimal precipitation conditions for the respective metal hydroxide, after addition an aqueous solution of a pre-condensate of melamine and formaldehyde, the mixture is intimately mixed, reacting for 0.5-3 hours at a temperature of 40 to 100 ° C and thereby allowing the pre-condensate to harden and finally drying the phosphor particles after filtration at an elevated temperature.
  • the final drying should advantageously be carried out at temperatures from 80 to 120 ° C. in a stream of nitrogen.
  • the molar ratio of melamine: formaldehyde in the precondensate can be from 1: 1 to 1: 6, preferably from 1: 1.2 to 1: 1.8.
  • the product listed under 1. is a partially etherified melamine / formaldehyde resin in the form of a 75% aqueous solution that has a dynamic viscosity of 300 - 500 mPa.s (at 23 ° C), a pH of 8.2 - 9.2 (at 23 ° C) and a density of 1.20 - 1.25 g / ml (at 23 ° C).
  • the melamine / formaldehyde resin listed under 2. is an uncured powder, the 50% aqueous solution of which has a dynamic viscosity of approx. 30 mPa ' s (at 20 ° C), a pH of 9 to 10 (at 20 ° C) and a density of 1.21 to 1.23 g / ml (at 20 ° C).
  • the hardening accelerator listed under 3. is an aqueous amine solution which has a pH of 6.2 - 7.0 (at 20 ° C), a density of 1.16 - 1.17 g / ml (at 20 ° C) and has a refractive index of 1.392-1.400 (at 25 ° C).
  • the oxidation stability was determined after a wet / warm storage test.
  • red phosphorus were weighed into a crystallizing dish with a diameter of 50 mm and the dish was stored in a closed glass vessel for 168 hours at 50 ° C. and 100% relative atmospheric humidity.
  • the resulting phosphorus was either expelled from the glass vessel by an air stream (10 J / h), reacted with 2.5% by mass mercury (II) chloride solution in a gas wash bottle and the amount of the hydrochloric acid formed was determined titrimetrically or with Detected with the help of a DR ⁇ GER tube "phosphorus 5o / a".
  • the phosphorus sample transferred to a 250 ml beaker, mixed with 200 ml of 1% hydrochloric acid, heated to boiling for 10 minutes and then filtered.
  • the acid-soluble phosphorus was then determined in the filtrate by the photometric molybdato-vanadato-phosphoric acid method.
  • the red phosphorus is subjected to the same analytical procedure without previous wet / warm storage. This value is then deducted when determining the content of acid-soluble phosphorus after wet / warm storage.
  • Example 2 The procedure was analogous to Example 1, but 3.0 g of aluminum hydroxide were used. An aluminum hydroxide content of 1.18% was determined in the analysis.
  • the melamine / formaldehyde resin content in the red phosphorus was 6.1%, which corresponds to a resin yield of 58%.
  • the melamine / formaldehyde resin content in the red phosphorus was 13.7%, which corresponds to a resin yield of 61%.
  • the melamine / formaldehyde resin content in the red phosphorus was 5.3%, which corresponds to a resin yield of 75%.
  • the melamine / formaldehyde resin content in the red phosphorus was 1 0, 7%, which corresponds to a resin yield of 71%.
  • a zinc hydroxide content of 0.91% was determined in the analysis.
  • a zinc hydroxide content of 1.75% was determined in the analysis.
  • a zinc hydroxide content of 4.65% was determined in the analysis.
  • Example 15 The procedure was analogous to Example 15, except that 5.7 g of cerium (III) nitrate and 34 g of ®Madurit MW 909 were used. The precipitation of the metal hydroxides and the condensation of the melamine resin were carried out at a pH of the phosphorus suspension of 8.
  • a manganese (11) hydroxide content of 1.00% was determined in the analysis.
  • a manganese (II) hydroxide content of 4.75% was determined in the analysis.
  • a manganese (II) hydroxide content of 0.94% and a melamine / formaldehyde resin content of 9.0% were determined in the analysis; this corresponds to a resin yield of 69%.
  • a manganese (II) hydroxide content of 2.82% and a melamine / formaldehyde resin content of 8.9% were determined in the analysis; this corresponds to a resin yield of 71%.
  • a silicon hydroxide content of 4.03% (calculated as SiO 2) was determined in the analysis.
  • the analysis determined a silicon hydroxide content of 1.02% (calculated as SiO 2 ) and a melamine / formaldehyde resin content of 8.6%; this corresponds to a resin yield of 80%.
  • a lead (II) hydroxide content of 1.44% was determined in the analysis.
  • a lead (II) hydroxide content of 4.17% was determined in the analysis.
  • a lead (II) hydroxide content of 3.90% and a melamine / formaldehyde resin content of 8.6% were determined in the analysis; this corresponds to a resin yield of 84%.
  • a chromium (III) hydroxide content of 1.37% and a melamine / formaldehyde resin content of 9.1% were determined in the analysis; this corresponds to a resin yield of 86%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Luminescent Compositions (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Fireproofing Substances (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
EP88102880A 1987-03-27 1988-02-26 Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung Expired - Lifetime EP0283759B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88102880T ATE54433T1 (de) 1987-03-27 1988-02-26 Stabilisierter roter phosphor sowie verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873710170 DE3710170A1 (de) 1987-03-27 1987-03-27 Stabilisierter roter phosphor sowie verfahren zu seiner herstellung
DE3710170 1987-03-27

Publications (2)

Publication Number Publication Date
EP0283759A1 EP0283759A1 (de) 1988-09-28
EP0283759B1 true EP0283759B1 (de) 1990-07-11

Family

ID=6324152

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88102880A Expired - Lifetime EP0283759B1 (de) 1987-03-27 1988-02-26 Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung

Country Status (10)

Country Link
US (1) US4853288A (zh)
EP (1) EP0283759B1 (zh)
JP (1) JP2759077B2 (zh)
CN (1) CN1016502B (zh)
AT (1) ATE54433T1 (zh)
CA (1) CA1334621C (zh)
DD (1) DD269374A5 (zh)
DE (2) DE3710170A1 (zh)
IN (1) IN170854B (zh)
NO (1) NO881345L (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8282751B2 (en) 2005-03-30 2012-10-09 Alliant Techsystems Inc. Methods of forming a sensitized explosive and a percussion primer
US8524018B2 (en) 2006-03-02 2013-09-03 Alliant Techsystems Inc. Percussion primers comprising a primer composition and ordnance including the same
US8540828B2 (en) 2008-08-19 2013-09-24 Alliant Techsystems Inc. Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same
US8641842B2 (en) 2011-08-31 2014-02-04 Alliant Techsystems Inc. Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2877821B2 (ja) * 1988-10-13 1999-04-05 日本化学工業株式会社 安定化赤リンおよびその製造法
JP2855331B2 (ja) * 1988-10-20 1999-02-10 日本化学工業株式会社 安定化赤リンおよびその製造方法
JP2835955B2 (ja) * 1988-10-20 1998-12-14 日本化学工業株式会社 安定化赤リンおよびその製造方法
DE3900965C1 (zh) * 1989-01-14 1989-10-19 Hoechst Ag, 6230 Frankfurt, De
DE4039905A1 (de) * 1990-12-14 1992-06-17 Hoechst Ag Stabilisierter roter phosphor sowie verfahren zu seiner herstellung
JP2601743B2 (ja) * 1992-02-18 1997-04-16 燐化学工業株式会社 微粉末状赤リン及びその製造方法
JP2832672B2 (ja) * 1993-08-12 1998-12-09 燐化学工業株式会社 赤リン系難燃剤及び難燃性樹脂組成物
US5543447A (en) * 1994-09-28 1996-08-06 Southwest Research Institute Stabilization of red amorphous phosphorus by ordered polymeric structures for the manufacture of non-emissive fire retardant plastics
FR2734256B1 (fr) * 1995-05-19 1997-07-04 Nyltech France Phosphore rouge stabilise, et son utilisation comme agent ignifugeant pour matieres plastiques
FR2734257B1 (fr) * 1995-05-19 1997-08-22 Nyltech France Phosphore rouge stabilise, et son utilisation comme agent ignifugeant pour matieres plastiques
DE10058922A1 (de) 2000-11-28 2002-06-06 Clariant Gmbh Stabilisierter roter Phosphor und ein Verfahren zu seiner Herstellung
DE10126760A1 (de) * 2001-06-01 2002-12-05 Bayer Ag Mikroverkapselter roter Phosphor
US8192568B2 (en) 2007-02-09 2012-06-05 Alliant Techsystems Inc. Non-toxic percussion primers and methods of preparing the same
US8202377B2 (en) 2007-02-09 2012-06-19 Alliant Techsystems Inc. Non-toxic percussion primers and methods of preparing the same
US8206522B2 (en) 2010-03-31 2012-06-26 Alliant Techsystems Inc. Non-toxic, heavy-metal free sensitized explosive percussion primers and methods of preparing the same
CN102010618B (zh) * 2010-11-19 2013-05-01 桐城市信得新材料有限公司 一种包覆红磷的制备方法
AU2013320577B2 (en) 2012-09-19 2016-06-16 Basf Se Flame-proofed polyamides with light colouring
CN110790247B (zh) * 2019-12-16 2021-10-08 湖北尧治河化工股份有限公司 一种用黄磷生产红磷的工艺

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2359243A (en) * 1943-08-13 1944-09-26 Oldbury Electro Chemical Co Treatment of phosphorus
US2635953A (en) * 1947-10-08 1953-04-21 Martin S Silverstein Inflammable compositions including red phosphorus
FR2314221A1 (fr) * 1975-06-10 1977-01-07 Rhone Poulenc Ind Compositions destinees a l'ignifugation de matieres plastiques
DE2622296C2 (de) * 1976-05-19 1984-12-06 Hoechst Ag, 6230 Frankfurt Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung
DE2631532C2 (de) * 1976-07-14 1984-09-13 Hoechst Ag, 6230 Frankfurt Stabilisierter pulverförmiger roter Phosphor sowie Verfahren zu seiner Herstellung
DE2632296C2 (de) * 1976-07-17 1979-02-01 Hoechst Ag, 6000 Frankfurt Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung
DE2646835C2 (de) * 1976-10-16 1984-11-15 Bayer Ag, 5090 Leverkusen Mikrogekapselter roter Phosphor als Brandschutzmittel für Polyamid-Formmassen
DE2647093C2 (de) * 1976-10-19 1984-12-06 Hoechst Ag, 6230 Frankfurt Stabilisierter pulverförmiger roter Phosphor sowie Verfahren zu seiner Herstellung
CA1097152A (en) * 1976-12-09 1981-03-10 Horst Staendeke Stabilized red phosphorus and process for making it
DE2705042A1 (de) * 1977-02-08 1978-08-10 Hoechst Ag Stabilisierter roter phosphor sowie verfahren zu seiner herstellung
DE2655739C2 (de) * 1976-12-09 1978-12-14 Hoechst Ag, 6000 Frankfurt Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung
DE2813151A1 (de) * 1978-03-25 1979-09-27 Hoechst Ag Stabilisierter roter phosphor
DE2945118C2 (de) * 1979-11-08 1981-12-03 Hoechst Ag, 6000 Frankfurt Stabilisierter roter Phosphor sowie Verfahren zu seiner Herstellung
US4525520A (en) * 1983-03-28 1985-06-25 Kanzaki Paper Manufacturing Company, Ltd. Method of preparing microcapsules
US4489183A (en) * 1983-12-13 1984-12-18 Erco Industries Limited Stabilization of red phosphorus
IT1200424B (it) * 1985-03-19 1989-01-18 Saffa Spa Fosforo rosso stabilizzato per uso come ritardante di fiamma,particolarmente per composizioni a base di polimeri
JPS6221704A (ja) * 1985-07-17 1987-01-30 Rin Kagaku Kogyo Kk 被覆赤リンの製造方法
JPH105996A (ja) * 1996-06-27 1998-01-13 Sony Corp 半田供給装置と半田液面変位測定方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8282751B2 (en) 2005-03-30 2012-10-09 Alliant Techsystems Inc. Methods of forming a sensitized explosive and a percussion primer
US8524018B2 (en) 2006-03-02 2013-09-03 Alliant Techsystems Inc. Percussion primers comprising a primer composition and ordnance including the same
US9199887B2 (en) 2006-03-02 2015-12-01 Orbital Atk, Inc. Propellant compositions including stabilized red phosphorus and methods of forming same
US8540828B2 (en) 2008-08-19 2013-09-24 Alliant Techsystems Inc. Nontoxic, noncorrosive phosphorus-based primer compositions and an ordnance element including the same
US8641842B2 (en) 2011-08-31 2014-02-04 Alliant Techsystems Inc. Propellant compositions including stabilized red phosphorus, a method of forming same, and an ordnance element including the same

Also Published As

Publication number Publication date
JP2759077B2 (ja) 1998-05-28
CN1016502B (zh) 1992-05-06
EP0283759A1 (de) 1988-09-28
NO881345D0 (no) 1988-03-25
ATE54433T1 (de) 1990-07-15
JPS63252912A (ja) 1988-10-20
DD269374A5 (de) 1989-06-28
DE3710170A1 (de) 1988-10-13
IN170854B (zh) 1992-05-30
US4853288A (en) 1989-08-01
DE3860298D1 (de) 1990-08-16
CA1334621C (en) 1995-03-07
CN88101594A (zh) 1988-10-05
NO881345L (no) 1988-09-28

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